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CN116515092A - Polyester polyol and preparation method and application thereof - Google Patents

Polyester polyol and preparation method and application thereof Download PDF

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Publication number
CN116515092A
CN116515092A CN202310529631.1A CN202310529631A CN116515092A CN 116515092 A CN116515092 A CN 116515092A CN 202310529631 A CN202310529631 A CN 202310529631A CN 116515092 A CN116515092 A CN 116515092A
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China
Prior art keywords
polyester polyol
dealcoholization
reaction
polyester
parts
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CN202310529631.1A
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Chinese (zh)
Inventor
郭逢霄
朱晓君
夏锋
张大华
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XUCHUAN CHEMICAL (SUZHOU) CO Ltd
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XUCHUAN CHEMICAL (SUZHOU) CO Ltd
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Priority to CN202310529631.1A priority Critical patent/CN116515092A/en
Publication of CN116515092A publication Critical patent/CN116515092A/en
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16—Dicarboxylic acids and dihydroxy compounds
    • C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
    • C08G63/181—Acids containing aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4205—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups
    • C08G18/4208—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups
    • C08G18/4211—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups derived from aromatic dicarboxylic acids and dialcohols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
    • C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4244—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups
    • C08G18/4247—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups derived from polyols containing at least one ether group and polycarboxylic acids
    • C08G18/425—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups derived from polyols containing at least one ether group and polycarboxylic acids the polyols containing one or two ether groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16—Dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/66—Polyesters containing oxygen in the form of ether groups
    • C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/672—Dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C09J175/06—Polyurethanes from polyesters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2101/00—Manufacture of cellular products
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2110/00—Foam properties
    • C08G2110/0025—Foam properties rigid

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Polyesters Or Polycarbonates (AREA)

Abstract

The invention relates to a polyester polyol and a preparation method and application thereof, wherein the raw materials for preparing the polyester polyol comprise the following components in parts by weight: 100 parts of polybasic acid, 100-300 parts of dealcoholization, 0-0.2 part of catalyst and not equal to 0 part; the hydroxyl value of the polyester polyol is 250-500KOH/g. The polyester polyol single kettle has high production quantity, stable product performance and high production efficiency, and can be used as raw materials of polyurethane rigid foam, adhesive and the like. The polyester polyols of the present invention based on dealcoholization are capable of providing close reactivity, foam density, foam mechanical strength and oxygen index when used in polyurethanes as compared to prior art industrial use of polyester polyols without aqueous raw materials.

Description

Polyester polyol and preparation method and application thereof
Technical Field
The invention relates to the technical field of polymer chemistry, in particular to a polyester polyol and a preparation method and application thereof.
Background
The production of polyester polyols involves two stages, esterification and polycondensation, in order to accelerate the reaction process, to increase the molecular weight of the product, to reduce the acid number (typically acid numbers require less than 1 mgKOH/g), and to prevent yellowing of the polyester, a vacuum of 0.1-10kPa is typically used in the polycondensation stage. This operation inevitably causes some of the polyol small molecules to be withdrawn from the reaction vessel together with byproduct water at 200 to 250 ℃. These small molecules of the polyol which are pumped away are usually called dealcoholization, and generally account for 3 to 15 percent of the input amount of the polyol monomer, and are placed in a storage tank. As the type and composition of the small molecules of the polyol used in the polyester polyol vary, the type, composition and water content of the small molecules of the polyol in the dealcoholization also fluctuate, and thus such dealcoholization is generally treated as liquid waste. In the prior art, the dealcoholization is usually collected and then reacted with the dibasic acid and polyol catalyst in a kettle.
CN104558548A discloses a method for preparing adipic acid polyester polyol by blending recycled alcohol condensate, which is characterized in that condensate collected from a condensation tank through a reaction condenser is put into a reaction kettle together with low molecular polyol, adipic acid and a catalyst to prepare adipic acid polyester polyol. But it does not relate to the stability of the product application.
In practice, the type, composition ratio and water content of the small molecules of the polyol in each dealcoholization batch are varied, and the variation can lead to unstable quality of the prepared polyester polyol product. Dealcoholized water content is generally between 10% and 40%, and such high water content can lead to reduced single kettle yield and low production efficiency.
It is therefore of great importance to develop a polyol based on dealcoholized polyester which is stable in properties and to increase its single pot yield.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a polyester polyol, a preparation method and application thereof, wherein the polyester polyol has high single kettle production, stable product performance and high production efficiency and can be used as raw materials of polyurethane rigid foam, adhesive and the like; the polyester polyols of the present invention based on dealcoholization are capable of providing close reactivity, foam density, foam mechanical strength and oxygen index when used in polyurethanes as compared to prior art industrial use of polyester polyols without aqueous raw materials.
To achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides a polyester polyol, which is prepared from the following raw materials in parts by weight:
100 parts of polybasic acid
Dealcoholizing 100-300 parts
0-0.2 parts of catalyst, and not equal to 0 parts;
the hydroxyl number of the polyester polyol is 250 to 500KOH/g, for example 250KOH/g, 300KOH/g, 350KOH/g, 400KOH/g, 450KOH/g, etc.
The polyester polyol products of the present invention based on dealcoholization are stable in performance and provide near reactivity, foam density, foam mechanical strength and oxygen index when used in polyurethanes as compared to prior art industries using polyester polyols without aqueous raw materials.
When the fluctuation of the kind and composition ratio of the small molecular polyol contained in the dealcoholization is large, the physical properties of the polyester polyol can be greatly changed when the hydroxyl value of the prepared polyester polyol is less than 250 mgKOH/g. For example, the same molecular weight, the product viscosity at room temperature typically varies by more than 10 times, even up to 100 times, and can change from a highly crystalline solid to an amorphous liquid, etc., which can affect downstream use. When the hydroxyl value of the polyester polyol is 250 mgKOH/g-500 mgKOH/g, the range of the product viscosity at normal temperature, which changes along with the change of the type and the composition of the polyol, is small, and the viscosity change range is small. The viscosity change is smaller with higher hydroxyl number and smaller with higher temperature. Such a universal product with varying polyol raw material composition but little viscosity variation is accepted in some polyurethane rigid foam, adhesive and coating applications. And as the hydroxyl value increases, more dealcoholization is needed for the product, the reaction time is shortened, and the occupation amount of dealcoholization in a factory is reduced.
In the present invention, the dealcoholized amount is 100 to 300 parts by weight, for example, 120 parts, 140 parts, 160 parts, 180 parts, 200 parts, 220 parts, 240 parts, 260 parts, 280 parts, etc.
The catalyst is 0 to 0.2 parts by weight and is not equal to 0 parts, for example 0.02 parts, 0.04 parts, 0.06 parts, 0.08 parts, 0.1 parts, 0.12 parts, 0.14 parts, 0.16 parts, 0.18 parts, etc.
Preferably, the dealcoholization comprises vacuum-removed polyol monomers as the polycondensation reaction proceeds in the production of polyester.
Preferably, the polyol monomers include any one or a combination of at least two of ethylene glycol, 1, 3-propanediol, 1, 2-propanediol, 1, 4-butanediol, diethylene glycol, triethylene glycol, methylpropanediol, 3-methyl-1, 5-pentanediol, neopentyl glycol, 1, 6-hexanediol, glycerol, or trimethylolpropane, wherein typical but non-limiting combinations include: a combination of ethylene glycol and 1, 3-propanediol, a combination of 1, 2-propanediol, 1, 4-butanediol and diethylene glycol, a combination of triethylene glycol, methylpropanediol, 3-methyl-1, 5-pentanediol and neopentyl glycol, a combination of methylpropanediol, 3-methyl-1, 5-pentanediol, neopentyl glycol, 1, 6-hexanediol, glycerol and trimethylolpropane, and the like.
Preferably, the dealcoholization also includes water removed in vacuo during polycondensation of polyester production.
Preferably, the polyacid comprises any one or a combination of at least two of succinic acid, adipic acid, sebacic acid, terephthalic acid, phthalic anhydride, isophthalic acid, or trimellitic anhydride, wherein typical but non-limiting combinations include: a combination of succinic acid, adipic acid and sebacic acid, a combination of terephthalic acid, phthalic anhydride, isophthalic acid and trimellitic anhydride, a combination of adipic acid, sebacic acid, terephthalic acid, phthalic anhydride and isophthalic acid, and the like.
Preferably, the catalyst comprises any one or a combination of at least two of stannous octoate, tetrabutyl titanate, or tetraisopropyl titanate, wherein typical but non-limiting combinations include: a combination of stannous octoate and tetrabutyl titanate, a combination of tetrabutyl titanate and tetraisopropyl titanate, a combination of stannous octoate, tetrabutyl titanate and tetraisopropyl titanate, and the like.
Preferably, the polyester polyol has an acid value of 3mgKOH/g or less, for example, 2.8mgKOH/g, 2.6mgKOH/g, 2.4mgKOH/g, 2.2mgKOH/g, 2.0mgKOH/g, etc.
In the present invention, the acid value of the polyester polyol is in a preferred range, and the reactivity thereof is relatively stable. When the acid value is less than or equal to 3mgKOH/g and the hydroxyl value is between 250 and 500mgKOH/g, the polycondensation stage of the production of the polyester polyol can be completed under normal pressure without high vacuum, thereby avoiding the production of new dealcoholization.
In a second aspect, the present invention provides a process for producing the polyester polyol according to the first aspect, comprising the steps of:
and under the action of a catalyst, sequentially carrying out dehydration reaction and polycondensation reaction on polybasic acid and dealcoholization in an inert atmosphere to obtain the polyester polyol.
Preferably, the temperature of the dehydration reaction is 140-200 ℃, e.g., 150 ℃, 160 ℃, 170 ℃, 180 ℃, 190 ℃, etc.;
preferably, the temperature of the polycondensation reaction is 200 to 250 ℃, e.g., 210 ℃, 220 ℃, 230 ℃, 240 ℃, etc.;
preferably, the dehydration reaction and the polycondensation reaction are carried out in a reaction kettle;
the reaction kettle is connected with a dealcoholization tank of other polyester reaction kettles, and dealcoholization is added into the system at least twice.
In the invention, in order to further improve the production efficiency, the number proportion of the reaction kettles connected with the reaction kettles for preparing the polyester polyol by using the dealcoholization and the conventional polyester polyol product can be designed according to the dealcoholization yield. Assuming that the volumes of the reaction kettles are the same, the average dealcoholized output of each kettle accounts for n% of the total feeding amount, the dealcoholized average water content is m%, and the number ratio of the connected reaction kettles of the conventional polyester polyol products to the reaction kettles for preparing the polyester polyol by dealcoholization is as follows:
when the ratio is smaller thanWhen the ratio is higher than that of the single kettle, the material is not fully charged, so that the yield of the single kettle is reducedIn the process, dealcoholization backlog can not be timely consumed.
The preparation method adopted by the invention specifically comprises the following steps:
(1) The reaction is started by adding a polybasic acid, dealcoholization and catalyst which at least satisfy the minimum production amount, and the dehydration reaction is performed under the protection of inert gas at 140 to 200 ℃ (e.g., 150 ℃, 160 ℃, 170 ℃, 180 ℃, 190 ℃ and the like), and then the polycondensation reaction is performed by raising the temperature to 200 to 250 ℃ (e.g., 210 ℃, 220 ℃, 230 ℃, 240 ℃ and the like).
(2) When a new dealcoholization is generated and put into a reaction vessel, a corresponding amount of polybasic acid is put together with a catalyst, and the reaction is directly carried out at 200 to 250 ℃ (e.g., 210 ℃, 220 ℃, 230 ℃, 240 ℃, etc.) until the designed production amount and acid value are lower than 3mgKOH/g (e.g., 2.8mgKOH/g, 2.6mgKOH/g, 2.4mgKOH/g, 2.2mgKOH/g, etc.), and the hydroxyl value is 250mgKOH/g to 500mgKOH/g (e.g., 300mgKOH/g, 350mgKOH/g, 400mgKOH/g, 450mgKOH/g, etc.).
The preparation method can stop the reaction after the last dealcoholization enters the reaction kettle for 4 hours.
Compared with the method that the total required amount of dealcoholization needed by waiting for producing one kettle of polyester polyol is collected and put into a reaction kettle to start reaction, the production method of the invention, which is carried out simultaneously by high-temperature reaction and continuous feeding, can improve the time efficiency, reduce the inventory occupation amount of dealcoholization in a factory and greatly improve the output of single kettle products.
In a third aspect, the present invention provides a polyester, the polyester comprising the polyester polyol of the first aspect as a starting material.
In a fourth aspect, the present invention provides the use of a polyester polyol according to the first aspect in a polyurethane rigid foam or adhesive.
Compared with the prior art, the invention has the following beneficial effects:
(1) The polyester polyol single kettle has high production quantity, stable product performance and high production efficiency, and can be used as raw materials of polyurethane rigid foam, adhesive and the like.
(2) The polyester polyols of the present invention based on dealcoholization are capable of providing close reactivity, foam density, foam mechanical strength and oxygen index when used in polyurethanes as compared to prior art industrial use of polyester polyols without aqueous raw materials.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
Example 1
The embodiment provides a polyester polyol, wherein the raw materials for preparing the polyester polyol comprise the following components: phthalic anhydride, dealcoholization and tetrabutyl titanate;
the dealcoholization 1 consists of 31% of water, 20% of ethylene glycol, 15% of 1, 4-butanediol and 34% of diethylene glycol; dealcoholization 2 is composed of 13% of water, 43% of 1, 4-butanediol and 44% of 1, 6-hexanediol, dealcoholization 3 is composed of 20% of water, 34% of ethylene glycol and 46% of diethylene glycol; dealcoholization 4 consisted of 35% water, 11% neopentyl glycol and 54% diethylene glycol; dealcoholization 5 consists of 38% water and 62% ethylene glycol; dealcoholization 6 is composed of 25% of water, 21% of ethylene glycol, 14% of propylene glycol and 40% of diethylene glycol; dealcoholization 7 consisted of 26% water, 43% ethylene glycol and 31% 1, 4-butanediol; dealcoholization 8 consisted of 23% water and 77% diethylene glycol; dealcoholization 9 consisted of 37% water, 15% ethylene glycol, 43% diethylene glycol and 5% 1, 6-hexanediol.
The polyester polyol is obtained by a preparation method comprising the following steps:
(1) 850g of phthalic anhydride, 1650g of dealcoholized 1 and 0.2g of tetrabutyl titanate are added into a 5 kg reaction kettle;
(2) Heating to 220 ℃ under the protection of nitrogen, then adding 170g of phthalic anhydride, 330g of dealcoholized 2 to dealcoholized 9 and 0.04g of tetrabutyl titanate into a reaction kettle every 20 minutes until the kettle is full, separating and removing the produced condensed water and micromolecular polyol by a fractionating tower connected with the reaction kettle, and stopping the reaction when the acid value is lower than 3mgKOH/g to obtain 4758g of polyester polyol with the hydroxyl value of 408mgKOH/g and the viscosity of 3890cPs/25 ℃.
Example 2
The embodiment provides a polyester polyol, wherein the raw materials for preparing the polyester polyol comprise the following components: phthalic anhydride, dealcoholization and tetrabutyl titanate;
the dealcoholization 10 consists of 18% water, 44% 1, 2-propanediol and 38% neopentyl glycol; dealcoholization 11 is composed of 27% of water, 12% of ethylene glycol, 33% of 1, 4-butanediol and 28% of diethylene glycol; dealcoholization 12 consists of 32% water, 23% 1, 2-propanediol, 31% 1, 4-butanediol and 14% neopentyl glycol; dealcoholization 13 is composed of 21% water, 30% ethylene glycol and 49% diethylene glycol; dealcoholization 14 is composed of 15% of water, 34% of 1, 4-butanediol and 51% of diethylene glycol; dealcoholization 15 consists of 28% water, 12% diethylene glycol and 60% neopentyl glycol; dealcoholization 16 consists of 15% water, 64% diethylene glycol and 21% neopentyl glycol; dealcoholization 17 consisted of 25% water and 75% neopentyl glycol; dealcoholization 18 consists of 19% water, 28% ethylene glycol and 53% 1, 2-propylene glycol.
The polyester polyol is obtained by a preparation method comprising the following steps:
(1) 900g of phthalic anhydride, 1600g of dealcoholized 10 and 0.2g of tetrabutyl titanate are taken and added into a 5 kg reaction kettle;
(2) Heating to 220 ℃ under the protection of nitrogen, then adding 180g of phthalic anhydride, 320g of dealcoholized 11 to 18 and 0.04g of tetrabutyl titanate into a reaction kettle every 20 minutes, and separating and removing the produced condensed water and micromolecular polyol by a fractionating tower connected with the reaction kettle. 144g of phthalic anhydride, 256g of dealcoholization and 0.032g of tetrabutyl titanate are added when the reaction kettle has 400g of raw material feeding space, and the reaction is stopped when the acid value is lower than 3mgKOH/g, so that 4812g of polyester polyol with the hydroxyl value of 418mgKOH/g and the viscosity of 3467cps/25 ℃ is finally obtained.
Example 3
The embodiment provides a polyester polyol, wherein the raw materials for preparing the polyester polyol comprise the following components: adipic acid, dealcoholization and tetrabutyl titanate;
the dealcoholization 19 consists of 22% water, 13% neopentyl glycol, 30% 1, 6-hexanediol and 35% methylpropanediol; dealcoholization 20 is composed of 35% water and 65% 1, 4-butanediol; dealcoholization 21 consists of 21% water, 36% 1, 4-butanediol and 43% 1, 6-hexanediol; dealcoholization 22 consists of 19% water, 62% diethylene glycol and 19% 1, 6-hexanediol; dealcoholization 23 consists of 19% water, 60% 1, 4-butanediol and 21% neopentyl glycol, 30% 1, 6-hexanediol and 35% methylpropanediol; dealcoholization 24 consists of 28% water, 24% diethylene glycol and 48% neopentyl glycol; dealcoholization 25 is composed of 20% of water, 11% of diethylene glycol and 69% of 1, 6-hexanediol; dealcoholization 26 consists of 21% water, 23% 1, 4-butanediol and 56% diethylene glycol; dealcoholization 27 consisted of 25% water, 5% 1, 4-butanediol and 70% neopentyl glycol.
The polyester polyol is obtained by a preparation method comprising the following steps:
(1) 1000g of adipic acid, 1500g of dealcoholized 19 and 0.2g of tetrabutyl titanate are taken and added into a 5 kg reaction kettle;
(2) Heating to 220 ℃ under the protection of nitrogen, then adding 200g of adipic acid, 300g of dealcoholized 20 to 27 and 0.04g of tetrabutyl titanate every 20 minutes into a reaction kettle, and separating and removing the produced condensed water and micromolecular polyol by a fractionating tower connected with the reaction kettle. 160g of adipic acid, 240g of dealcoholized alcohol and 0.032g of tetrabutyl titanate are added when a 400g raw material feeding space is provided in the reaction kettle, and the reaction is stopped when the acid value is lower than 3mgKOH/g, so that 4823g of polyester polyol with the hydroxyl value of 252mgKOH/g and the viscosity of 1735cps/25 ℃ is finally obtained.
Example 4
This example differs from example 1 in that the dealcoholization is collected uniformly after the dealcoholization in the dealcoholization tank connected to the reaction vessel in example 1, and the dealcoholization 28 is composed of 29% of water, 21% of ethylene glycol, 11% of 1, 4-butanediol, 33% of diethylene glycol, 1% of 1, 2-propanediol, 1% of neopentyl glycol and 4% of 1, 6-hexanediol.
The polyester polyol is obtained by a preparation method comprising the following steps:
(1) 850g of phthalic anhydride, 1650g of dealcoholized 28 and 0.2g of tetrabutyl titanate were charged into a 5 kg reaction vessel;
(2) Heating to 220 ℃ under the protection of nitrogen, then adding 170g of phthalic anhydride, 330g of dealcoholized 28 and 0.04g of tetrabutyl titanate into a reaction kettle every 20 minutes until the kettle is full, separating and removing the produced condensed water and micromolecular polyol by a fractionating tower connected with the reaction kettle, and stopping the reaction when the acid value is lower than 3mgKOH/g, thus obtaining 4683g of polyester polyol with the hydroxyl value of 419mgKOH/g and the viscosity of 3656cPs/25 ℃.
Example 5
The embodiment provides a polyester polyol, wherein the raw materials for preparing the polyester polyol comprise the following components: phthalic anhydride, dealcoholization and tetrabutyl titanate;
the dealcoholization 28 consists of 29% water, 21% ethylene glycol, 11% 1, 4-butanediol, 33% diethylene glycol, 1, 2-propanediol, 1% neopentyl glycol and 4% 1, 6-hexanediol.
The polyester polyol is obtained by a preparation method comprising the following steps:
(1) 1700g of phthalic anhydride, 3300g of dealcoholized 28 and 0.4g of tetrabutyl titanate are taken and added into a 5 kg reaction kettle;
(2) Heating to 220 ℃ under the protection of nitrogen, and separating and removing the produced condensed water and micromolecular polyol by a fractionating tower connected with a reaction kettle. When the acid value was less than 3mgKOH/g, the reaction was stopped to finally obtain 3687g of a polyester polyol having a hydroxyl value of 420mgKOH/g and a viscosity of 3775cPs/25 ℃.
Example 6
The embodiment provides a polyester polyol, wherein the raw materials for preparing the polyester polyol comprise the following components: phthalic anhydride, dealcoholization and tetrabutyl titanate;
this example differs from example 2 in that the dealcoholization is collected uniformly after the dealcoholization by the dealcoholization tank connected to the reaction vessel in example 2, and the dealcoholization 29 is composed of 21% of water, 5% of ethylene glycol, 23% of 1, 2-propanediol, 8% of 1, 4-butanediol, 16% of diethylene glycol and 28% of neopentyl glycol.
The polyester polyol is obtained by a preparation method comprising the following steps:
(1) 1800g of phthalic anhydride, 3200g of dealcoholized 29 and 0.4g of tetrabutyl titanate are taken and added into a 5 kg reaction kettle;
(2) Heating to 220 ℃ under the protection of nitrogen, and separating and removing the produced condensed water and micromolecular polyol by a fractionating tower connected with a reaction kettle. When the acid value was less than 3mgKOH/g, the reaction was stopped to finally obtain 4035g of a polyester polyol having a hydroxyl value of 412mgKOH/g and a viscosity of 3610cPs/25 ℃.
Example 7
The embodiment provides a polyester polyol, wherein the raw materials for preparing the polyester polyol comprise the following components: adipic acid, dealcoholization and tetrabutyl titanate;
this example differs from example 3 in that the dealcoholization is collected uniformly after dealcoholization in the dealcoholization tank connected to the reaction vessel in example 3, and the dealcoholization 30 is composed of 23% of water, 15% of 1, 4-butanediol, 12% of diethylene glycol, 16% of neopentyl glycol, 21% of 1, 6-hexanediol and 13% of methylpropanediol.
The polyester polyol is obtained by a preparation method comprising the following steps:
(1) 2000g of adipic acid, 3000g of dealcoholized 30 and 0.4g of tetrabutyl titanate are taken and added into a 5 kg reaction kettle;
(2) Heating to 220 ℃ under the protection of nitrogen, and separating and removing the produced condensed water and micromolecular polyol by a fractionating tower connected with a reaction kettle. The reaction was stopped at a value of less than 3mgKOH/g to finally obtain 3593g of a polyester polyol having a hydroxyl value of 255mgKOH/g and a viscosity of 1833cPs/25 ℃.
Comparative example 1
The comparative example provides a polyester polyol, the raw materials for preparing the polyester polyol comprise the following components: phthalic anhydride, ethylene glycol, diethylene glycol and tetrabutyl titanate;
the polyester polyol is obtained by a preparation method comprising the following steps:
(1) Adding 2140g of phthalic anhydride, 720g of ethylene glycol, 2140g of diethylene glycol and 0.4g of tetrabutyl titanate into a 5 kg reaction kettle;
(2) Heating to 220 ℃ under the protection of nitrogen, and separating and removing the produced condensed water and micromolecular polyol by a fractionating tower connected with a reaction kettle. When the acid value was less than 3mgKOH/g, the reaction was stopped to finally obtain 4496g of a polyester polyol having a hydroxyl value of 397mgKOH/g and a viscosity of 1910cPs/25 ℃.
Comparative example 2
This comparative example differs from example 1 in that the hydroxyl value of the polyester polyol is 197mgKOH/g, specifically as follows:
the preparation raw materials of the polyester polyol comprise the following components: phthalic anhydride, dealcoholization and tetrabutyl titanate;
the dealcoholization 28 consists of 29% water, 21% ethylene glycol, 11% 1, 4-butanediol, 33% diethylene glycol, 1% 1, 2-propanediol, 1% neopentyl glycol and 4% 1, 6-hexanediol
The polyester polyol is obtained by a preparation method comprising the following steps:
(1) 1100g of phthalic anhydride, 1400g of dealcoholized 28 and 0.2g of tetrabutyl titanate are added into a 5 kg reaction kettle;
(2) Heating to 220 ℃ under the protection of nitrogen, then adding 220g of phthalic anhydride 170g, 280g of dealcoholized 28 and 0.04g of tetrabutyl titanate into a reaction kettle every 20 minutes until the kettle is full, separating and removing the produced condensed water and micromolecular polyol by a fractionating tower connected with the reaction kettle, and stopping the reaction when the acid value is lower than 3mgKOH/g, thus obtaining 4683g of polyester polyol with the hydroxyl value of 197mgKOH/g and the viscosity of 218770cPs/25 ℃.
Comparative example 3
This comparative example differs from example 1 in that the hydroxyl value of the polyester polyol is 550mgKOH/g, specifically as follows:
the preparation raw materials of the polyester polyol comprise the following components: phthalic anhydride, dealcoholization and tetrabutyl titanate;
the dealcoholization 28 consists of 29% water, 21% ethylene glycol, 11% 1, 4-butanediol, 33% diethylene glycol, 1, 2-propanediol, 1% neopentyl glycol and 4% 1, 6-hexanediol.
The polyester polyol is obtained by a preparation method comprising the following steps:
(1) 730g of phthalic anhydride, 1770g of dealcoholized 28 and 0.2g of tetrabutyl titanate are added into a 5 kg reaction kettle;
(2) Heating to 220 ℃ under the protection of nitrogen, then adding 146g of phthalic anhydride, 354g of dealcoholized 28 and 0.04g of tetrabutyl titanate into a reaction kettle every 20 minutes until the kettle is full, separating and removing the produced condensed water and micromolecular polyol by a fractionating tower connected with the reaction kettle, and stopping the reaction when the acid value is lower than 3mgKOH/g, thus obtaining 4782g of polyester polyol with the hydroxyl value of 558mgKOH/g and the viscosity of 473cPs/25 ℃.
Performance testing
1. The polyester polyols described in examples 1-7 and comparative examples 1-3 were tested as follows:
(1) Single pot yield (%): is the weight ratio of the output to the full kettle charge.
(2) Hydroxyl number (mgKOH/g): reference is made to the procedure specified in HG/T2709-1995.
(3) Viscosity (cps) at 25 ℃): reference is made to the procedure specified in GB/T22235-2008.
The test results are summarized in table 1.
TABLE 1
As can be seen from an analysis of the data in Table 1, the polyester polyol according to the present invention has a one pot yield of 72% or more and a viscosity of 1735-3890cPs at 25 ℃.
Within the preferred range (examples 1-4) the polyester polyols of the present invention have a one pot yield of 94% or more and a viscosity of 1735-3890cPs at 25 ℃.
The dealcoholization with water is generally used to prepare polyester polyol with the hydroxyl value of 250 mgKOH/g-500 mgKOH/g and the yield of 60% -85%, assuming that a reaction kettle of 20 tons is used, the dealcoholization produced in each kettle is 1 ton, if the dealcoholization is one-time put into a production kettle of 20 tons, the weight of the finally produced product is 12-17 tons. If the batch feeding is carried out, the weight of the final product can reach 19.2 to 19.7 tons calculated by the feeding amount of the last batch of dealcoholization and dibasic acid being 2 tons.
Analysis of comparative example 1 with example 1 shows that the dealcoholized polyester polyol of the present invention provides close single pot yields, viscosities and hydroxyl values as compared to the polyester polyol of comparative example 1.
Analysis of comparative examples 2-3 and example 1 revealed that too high or too low a viscosity of comparative examples 2-3 would affect the application and the properties were inferior to those of example 1, demonstrating that the polyester polyol hydroxyl value was better in the range of 250-500 mgKOH/g.
Analysis of examples 5 and 1, examples 6 and 2, and examples 7 and 3 shows that the polyester polyol products with close hydroxyl values are produced without changing the composition ratio of the fed materials, and the continuous feeding is performed at high temperature while the single kettle yield is high and the viscosity change is small compared with the single kettle produced by one-time feeding.
2. The polyester polyols described in examples 1-2 and comparative example 1 were formed into polyurethanes, and tested for foaming properties, compressive strength, free foam density using test methods referred to: GB/T8813-2020, test methods for oxygen index are described with reference to: GB/T2409.2-2009.
Specifically, the preparation method of the polyurethane comprises the following steps:
100 parts by mass of a polyester polyol, 15 parts by mass of TCPP, and silicone oil (trade nameB8462 2 parts by mass, 1 part by mass of water, and an amine catalyst (trade name +.>8) 0.5 part by mass and a potassium salt catalyst (trade name ++>K-15) 1 part by mass, 12 parts by mass of n-pentane as a foaming agent, and 190 parts by mass of polymethylene polyphenyl isocyanate (trade name WANNATE PM-200) to obtain the polyurethane.
The test results are summarized in Table 2.
TABLE 2
Foam Properties Example 1 Example 2 Comparative example 1
Heuristic time (seconds) 25 26 24
Gel time (seconds) 52 50 52
Free bubble density (kg/cubic meter) 46 45 45
Compressive Strength (kilopascals) 246 257 252
Oxygen index (%) 25.2 25.1 25.1
From an analysis of the data in Table 2, it can be seen that the dealcoholized polyester polyol according to the present invention is capable of providing close reactivity, foam density, foam mechanical strength and oxygen index as compared with the polyester polyol of comparative example 1.
The present invention is described in detail by the above examples, but the present invention is not limited to the above detailed methods, i.e., it does not mean that the present invention must be practiced depending on the above detailed methods. It should be apparent to those skilled in the art that any modification of the present invention, equivalent substitution of raw materials for the product of the present invention, addition of auxiliary components, selection of specific modes, etc., falls within the scope of the present invention and the scope of disclosure.

Claims (10)

1. The polyester polyol is characterized by comprising the following raw materials in parts by weight:
100 parts of polybasic acid
Dealcoholizing 100-300 parts
0-0.2 parts of catalyst, and not equal to 0 parts;
the hydroxyl value of the polyester polyol is 250-500KOH/g.
2. The polyester polyol according to claim 1, wherein the dealcoholization comprises vacuum-removed polyol monomers in the polycondensation reaction of polyester production;
the polyol monomer comprises any one or a combination of at least two of ethylene glycol, 1, 3-propylene glycol, 1, 2-propylene glycol, 1, 4-butanediol, diethylene glycol, triethylene glycol, methyl propylene glycol, 3-methyl-1, 5-pentanediol, neopentyl glycol, 1, 6-hexanediol, glycerol or trimethylolpropane;
the dealcoholization also comprises water which is removed in vacuum during the polycondensation reaction in the production of polyester.
3. The polyester polyol according to claim 1, wherein the polyacid comprises any one or a combination of at least two of succinic acid, adipic acid, sebacic acid, terephthalic acid, phthalic anhydride, isophthalic acid, or trimellitic anhydride.
4. The polyester polyol according to claim 1, wherein the catalyst comprises any one or a combination of at least two of stannous octoate, tetrabutyl titanate, or tetraisopropyl titanate.
5. The polyester polyol according to claim 1, wherein the acid value of the polyester polyol is 3mgKOH/g or less.
6. A process for the preparation of a polyester polyol according to any one of claims 1 to 5, comprising the steps of:
and under the action of a catalyst, sequentially carrying out dehydration reaction and polycondensation reaction on polybasic acid and dealcoholization in an inert atmosphere to obtain the polyester polyol.
7. The method according to claim 6, wherein the dehydration reaction is carried out at a temperature of 140 to 200 ℃.
8. The process according to claim 6, wherein the polycondensation reaction is carried out at a temperature of 200 to 250 ℃.
9. The method according to claim 6, wherein the dehydration reaction and the polycondensation reaction are performed in a reaction vessel;
the reaction kettle is connected with a dealcoholization tank of other polyester reaction kettles, and dealcoholization is added into the system at least twice.
10. Use of the polyester polyol according to any of claims 1 to 5 in polyurethane rigid foams or adhesives.
CN202310529631.1A 2023-05-11 2023-05-11 Polyester polyol and preparation method and application thereof Pending CN116515092A (en)

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